DOE OSTI2017
The overall goal of the project was to demonstrate solvent liquefaction as a viable path to stable intermediates for subsequent upgrading to fuel blendstocks. Iowa State University (ISU) utilized technology developed by Chevron to produce “green crude” via continuous biomass liquefaction to bio-oil without catalyst or reducing gas, then upgraded the crude to drop-in hydrocarbon liquid transportation fuels. Original benchmarks for the project included conversion of biomass to bio-oil at a yield of 50% or more, produce bio-oil with oxygen content below 20 wt%, and recycle a portion of the bio-oil product for use as solvent, displacing initial hydrocarbon solvent. Initial testing and technology development was completed by Chevron using a custom Small Continuous Liquefaction Unit (SCLU) operated in “once-through” mode. In this system, liquid product and solid residual/char was collected together and required both off-line solids removal and product separation. This unit was disassembled and major components incorporated into a redesigned solvent liquefaction system at ISU capable of processing biomass at rates up to 1 kg/h. Online, continuous solids separation and bio-oil recovery/separation systems were successfully implemented. Online solids removal using an acetone injection to aid in separation achieved over 99% solids removal efficiency, and acetone recovery of greater than 97% was achieved. The gas stripping system developed for the separation of medium wood oil (MWO) for the recycle stream from the heavy wood oil (HWO) product stream was also successful in recovering approximately 93 wt% of the initial solvent from the biomass-derived products. Due to the generation of fine particulate and the high molecular weight of the HWO which both negatively affect the ability to separate the product oil, solvent recycle was not fully implemented in the system. The biomass used in this project is loblolly pine forest residue. The solvent was a blend of two hydrocarbon liquids. The majority of the solvent was comprised of commercially available naphthalene-depleted heavy aromatic solvent. The hydrogen donor solvent was a proprietary cut of light cycle oil (LCO) that was hydrotreated. As much as 25 wt% of the solvent mixture was comprised of the hydrotreated LCO. Higher blend ratios were limited by the economics of providing hydrogen to the process in this manner. Two cases were evaluated for technical feasibility on the SCLU. These are 1. Simulated phenolic solvent recycle and 2. Hydrocarbon-rich solvent processing. The simulated phenolic solvent recycle case was based on an idealistic solvent mixture where only 5% makeup or hydrogen donor solvent entered the system. The resulting solvent mixture at steady state was estimated to be 75 wt% depleted hydrogen donor, 20 wt% biomass derived phenolic monomers, and 5 wt% HLCO. This case resulted in the highest bio-oil organic yield observed in the project of 66.7 wt% on a solvent-less, dry biomass basis and relatively low oxygen content of 12%. Additionally, these conditions deconstructed the biomass so well, that extremely fine particulate was generated such that 5 micron barrier filters were unable to remove the material. Offline addition of acetone, centrifugation and acetone removal were required in order to remove the particulate prior to fractionation with the stripping column. The resulting HWO had a high molecular weight and was therefore very viscous in nature, remaining solid at room temperature. Additionally, the column was unable to sustainably strip enough MWO to close the recycle loop balance while maintaining flowability of product oil exiting the column. It was determined that additional HLCO would be required at the front of the process to decrease product viscosity both by dilution and additional hydrogen transfer into the HWO product oil. The hydrocarbon rich mixture was the preferred mixture for a majority of the project and featured a 25% donor or HLCO content and 75% depleted hydrogen donor mix. A series of three tests were conducted using this mixture and serve as the basis for a paper detailing the system. While the online acetone injection system for high pressure solids removal was demonstrated early on using this mixture, difficulty controlling process flows led to the use of an atmospheric stirred tank filtration system. At these high donor solvent levels, the product stream easily partitioned with sufficient MWO to close the recycle loop balance. Additionally, this mixture produced HWO product oil at just over 55% yield, <5% oxygen content, and a reasonable viscosity at room temperature. A 56 hour campaign was conducted with the ISU pilot to produce a large enough batch of HWO product oil to conduct upgrading experiments at Chevron’s Richmond, CA facility. Benchtop hydrotreating units were used to conduct long-duration hydrogenation/hydrogenolysis reactions in order to provide yield data and help validate assumptions made in the TEA model. Resulting products featured an oxygen content of <1%, near the detectability limit. Hydrocracking simulations were also performed, and a distribution of heavy wood oil to refinery products was determined. These distributions are based on a database of commercial and pilot plant operation used by Chevron to estimate product yield from novel inputs based on the input physical and chemical characteristics. While multi-week benchtop hydrotreating tests were successfully conducted without fouling, analysis and testing of the heavy wood oil suggest it may be better suited for hydrocracking. Metals content in the heavy wood oil would likely create catalyst fouling over time and reduce lifetime of hydrotreating catalysts. Yields and product partitioning were also more favorable from hydrocracking compared to those from hydrotreating.